Alkoxylated unsaturated fatty acids and uses thereof

ABSTRACT

Alkoxylated fatty acids are disclosed herein, as well as methods of making and using such compounds. In some embodiments, the alkoxylated fatty acids are formed from monomers derived from natural oils. In some embodiments, the alkoxylated fatty acids are used as surfactants for making synthetic latex by emulsion polymerization. In some other embodiments, the alkoxylated fatty acids are used as surfactants for making synthetic rubber, such as styrene-butadiene rubber. In some other embodiments, the alkoxylated fatty acids are used as surfactants in a composition for treatment of gas or oil wells, for cleaning applications, for use in various laundry-related applications, for use in personal care compositions, or for use as solvents for coating applications, such as reactive and non-reactive waterborne coating applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is continued application of Ser. No. 15/419,185 filedJan. 30, 2017, now U.S. Pat. No. 10,100137, which claims benefit ofpriority of United States Provisional Application Nos. 62/290,815, filedFeb. 3, 2016, and 62/305,563, filed Mar. 9, 2016, both of which arehereby incorporated by reference as though set forth herein in theirentirety.

TECHNICAL FIELD

Alkoxylated fatty acids are disclosed herein, as well as methods ofmaking and using such compounds. In some embodiments, the alkoxylatedfatty acids are formed from monomers derived from natural oils. In someembodiments, the alkoxylated fatty acids are used as surfactants formaking synthetic latex by emulsion polymerization. In some otherembodiments, the alkoxylated fatty acids are used as surfactants formaking synthetic rubber, such as styrene-butadiene rubber. In some otherembodiments, the alkoxylated fatty acids are used as surfactants in acomposition for treatment of gas or oil wells, for cleaningapplications, for use in various laundry-related applications, for usein personal care compositions, or for use as solvents for coatingapplications, such as reactive and non-reactive waterborne coatingapplications.

BACKGROUND

Synthetic latexes are commonly made by emulsion polymerization. Incertain emulsion polymerization processes, monomer compounds aresuspended within an aqueous medium as part of micelles that are formedwith the assistance of a surfactant. The polymerization reactions insuch systems generally proceed by free radical polymerization. When thepolymerization is complete, the resulting polymer can be removed fromthe aqueous medium. Or, in other instances, the resulting dispersion isthe end product.

Emulsion polymerization presents a number of advantages as a method ofmaking certain latexes by free radical polymerization. For example, theprocess allows for rapid polymerization in a temperature-controlledenvironment. Therefore, the properties of the resulting polymer do notchange as the reaction proceeds and heat is generated. Further, emulsionpolymerization permits the reaction medium to retain a near-constantviscosity, which also prevents the properties from changing as thereaction proceeds.

One drawback, however, is that the surfactants that enable thepolymerization remain in the composition following the reaction. Thesesurfactants can be difficult to remove from the polymer composition.Therefore, it may be desirable to discover surfactant compounds thathave a sufficiently low critical micelle concentration and that do notrequire intensive removal efforts following polymerization.

Thus, there is a continuing need to discover novel surfactants that canserve such purposes and improve the properties of the polymers made byemulsion polymerization.

SUMMARY

In a first aspect, the disclosure provides compounds of formula (I):

wherein: R¹ is a hydrogen atom or C₁₋₆ alkyl; G¹ is C₁₋₄ alkylene; R² isa hydrogen atom, C₁₋₅ alkyl, or C₂₋₅ alkenyl; and n is an integer from 1to 50. In some embodiments, n is an integer from 6 to 50.

In a second aspect, the disclosure provides compositions comprising:water and one or more compounds of the first aspect. In someembodiments, the compositions further comprise one or more monomers,such as monomers suitable for forming synthetic latex materials usingemulsion polymerization, or monomers suitable for forming a syntheticrubber, such as a styrene-butadiene rubber. In some embodiments, the oneor monomers include vinyl compounds, acrylates, and various combinationsthereof.

In a third aspect, the disclosure provides polymer compositions, whichare formed from a reaction mixture, wherein the reaction mixture is acomposition of any embodiments of the second aspect.

In a fourth aspect, the disclosure provides methods of forming a polymercomposition, the methods comprising: providing a composition of anyembodiments of the second aspect, such as those that include one or moremonomers; and reacting the one or more monomers in the composition toform the polymer composition.

In a fifth aspect, the disclosure provides compositions comprising:water and one or more compounds of the first aspect, where thecomposition is suitable for use in treating an oil or gas well, forexample, in combination with other materials, such as various terpenes(e.g., d-limonene) or saturated and/or unsaturated esters (e.g., methyl9-decenoate, methyl 9-dodecenoate, and the like).

In a sixth aspect, the disclosure provides cleaning compositionscomprising: water and one or more compounds of the first aspect, wherethe composition is suitable for use in various cleaning applications,such as hard-surface cleaning, and the like. In some such aspects, thedisclosure provides methods of cleaning comprising: providing acomposition comprising water and one or more compounds of the firstaspect; and applying the composition to a surface to be cleaned. In someembodiments, the surface is a hard surface.

In a seventh aspect, the disclosure provides fabric care compositionscomprising: water and one or more compounds of the first aspect, wherethe composition is suitable for use in various fabric-care applications,such as in laundry detergents, fabric softeners, and the like. In somesuch aspects, the disclosure provides methods for treating fabric,comprising: providing a composition comprising water and one or morecompounds of the first aspect; and applying the composition to a fabricarticle.

In an eighth aspect, the disclosure provides personal care compositionscomprising: water and one or more compounds of the first aspect, wherethe composition is suitable for use in various personal careapplications. In some embodiments, the compositions are in the form ofan emulsion, such as an oil-in-water or a water-in-oil emulsion. In somesuch aspects, the disclosure provides methods for treating mammalianskin or hair, comprising: providing a composition comprising water andone or more compounds of the first aspect; and applying the compositionto mammalian skin or hair. In some embodiments, the mammalian skin orhair is human skin or hair.

In a ninth aspect, the disclosure provides coating compositionscomprising: water, a resin, and one or more compounds of the firstaspect. In some embodiments, the resin is a film-forming polymer. Insome such embodiments, the film-forming polymer is a natural orsynthetic latex. In some other embodiments, the resin is an alkyd resin.In some such aspects, the disclosure provides methods for coating asurface, comprising: providing a composition comprising water, a resin,and one or more compounds of the first aspect; and applying thecomposition to a surface to be coated. In some embodiments, the resin isa film-forming polymer. In some other embodiments, the resin is an alkydresin.

In certain other aspects, the disclosure provides various compositionsand methods that employ compounds of the first aspect. These and otheraspects and embodiments are set forth in the foregoing drawings,detailed description, and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

The FIGURE shows a compound of certain aspects and embodiments disclosedherein, wherein R¹ is a hydrogen atom or an alkyl group; G¹ is analkylene group; R² is a hydrogen atom, an alkyl group, or an alkenylgroup; and n is an integer from 1 to 50.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “polymer” refers to a substance having a chemicalstructure that includes the multiple repetition of constitutional unitsformed from substances of comparatively low relative molecular massrelative to the molecular mass of the polymer. The term “polymer”includes soluble and/or fusible molecules having chains of repeat units,and also includes insoluble and infusible networks. As used herein, theterm “polymer” can include oligomeric materials, which have only a few(e.g., 5-100) constitutional units

As used herein, “monomer” refers to a substance that can undergo apolymerization reaction to contribute constitutional units to thechemical structure of a polymer.

As used herein, “copolymer” refers to a polymer having constitutionalunits formed from more than one species of monomer.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins includealpha-olefins, wherein the unsaturated carbon-carbon bond is present atone end of the compound. Low-molecular-weight olefins may also includedienes or trienes. Low-molecular-weight olefins may also includeinternal olefins or “low-molecular-weight internal olefins.” In certainembodiments, the low-molecular-weight internal olefin is in the C₄₋₁₄range. Examples of low-molecular-weight olefins in the C₂₋₆ rangeinclude, but are not limited to: ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1,4-pentadiene,1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, andcyclohexene. Non-limiting examples of low-molecular-weight olefins inthe C₇₋₉ range include 1,4-heptadiene, 1-heptene, 3,6-nonadiene,3-nonene, 1,4,7-octatriene. Other possible low-molecular-weight olefinsinclude styrene and vinyl cyclohexane. In certain embodiments, it ispreferable to use a mixture of olefins, the mixture comprising linearand branched low-molecular-weight olefins in the C₄₋₁₀ range. Olefins inthe C₄₋₁₀ range can also be referred to as “short-chain olefins,” whichcan be either branched or unbranched. In one embodiments, it may bepreferable to use a mixture of linear and branched C₄ olefins (i.e.,combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C₁₁₋₁₄ may be used.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms; and “C_(x-y)”, which refers to a group or compoundcontaining from x to y, inclusive, carbon atoms. For example, “C₁₋₆alkyl” represents an alkyl chain having from 1 to 6 carbon atoms and,for example, includes, but is not limited to, methyl, ethyl, n-propyl,isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl,n-pentyl, neopentyl, and n-hexyl. As a further example, a “C₄₋₁₀ alkene”refers to an alkene molecule having from 4 to 10 carbon atoms, and, forexample, includes, but is not limited to, 1-butene, 2-butene, isobutene,1-pentene, 1-hexene, 3-hexene, 1-heptene, 3-heptene, 1-octene, 4-octene,1-nonene, 4-nonene, and 1-decene.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin ester”or “olefinic ester compounds.” Further, a “terminal olefinic estercompound” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y) alkyl,” which refersto an alkyl group, as herein defined, containing from x to y, inclusive,carbon atoms. Thus, “C₁₋₆ alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group.

As used herein, “alkenyl” refers to a straight or branched chainunsaturated hydrocarbon having 2 to 30 carbon atoms and one or morecarbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-butenyl, 2-pentenyl,3-hexenyl, and the like. The number of carbon atoms in an alkenyl groupis represented by the phrase “C_(x-y) alkenyl,” which refers to analkenyl group, as herein defined, containing from x to y, inclusive,carbon atoms. Thus, “C₂₋₆ alkenyl” represents an alkyl chain having from2 to 6 carbon atoms and, for example, includes, but is not limited to,vinyl, allyl, 2-butenyl, 3-butenyl, 1-butenyl, 2-pentenyl, 3-hexenyl,and the like. In some instances, the “alkenyl” group can be divalent, inwhich case the group can alternatively be referred to as an “alkenylene”group.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week, or a compound which maintains its integrity long enoughto be useful for therapeutic or prophylactic administration to apatient. As used herein, the phrases “substituted with one or more . . .” or “substituted one or more times . . . ” refer to a number ofsubstituents that equals from one to the maximum number of substituentspossible based on the number of available bonding sites, provided thatthe above conditions of stability and chemical feasibility are met.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

In some instances herein, organic compounds are described using the“line structure” methodology, where chemical bonds are indicated by aline, where the carbon atoms are not expressly labeled, and where thehydrogen atoms covalently bound to carbon (or the C—H bonds) are notshown at all. For example, by that convention, the formula

represents n-propane. In some instances herein, a squiggly bond is usedto show the compound can have any one of two or more isomers. Forexample, the structure

can refer to (E)-2-butene, (Z)-2-butene, or mixtures thereof. In someembodiments, the compounds disclosed herein are generated via olefinmetathesis from natural oils, which can result in scrambling of thestereochemistry around the carbon-carbon double bond, creating a mixtureof E and Z compounds (where R² is not a hydrogen atom). In someembodiments herein, which contain compounds of formula (I) and where R²is not a hydrogen atom, the composition comprises at least 1% by weight,or at least 2% by weight, or at least 5% by weight, or at least 10% byweight, or at least 20% by weight, or at least 35% by weight, or atleast 50% by weight, or at least 65% by weight, or at least 75% byweight, of compounds of formula (I) where the substituents on thecarbon-carbon double bond are in the E (trans) configuration, based onthe total weight of compounds of formula (I) in the composition.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Alkoxylated Unsaturated Fatty Acid Compounds

In a first aspect, the disclosure provides compounds of formula (I):

wherein: R¹ is a hydrogen atom or C₁₋₆ alkyl; G¹ is C₁₋₄ alkylene; R² isa hydrogen atom, C₁₋₅ alkyl, or C₂₋₅ alkenyl; and n is an integer from 1to 50.

In some embodiments, R¹ is a hydrogen atom. In some other embodiments ofany of the aforementioned embodiments, R¹ is C₁₋₆ alkyl. In some suchembodiments, R¹ is methyl or ethyl. In some such embodiments, R¹ ismethyl. In some other such embodiments, R¹ is ethyl.

In some embodiments of any of the aforementioned embodiments, G¹ is,independently at each occurrence, —CH₂—CH₂—, —CH₂—CH₂—CH₂—,—CH(CH₃)—CH₂—, —CH₂—CH(CH₃)—, or —CH₂—CH₂—CH₂—CH₂—. In some suchembodiments, G¹ is —CH₂—CH₂.

In some embodiments of any of the aforementioned embodiments, R² is ahydrogen atom. In some other embodiments of any of the aforementionedembodiments, R² is C₁₋₅ alkyl. In some such embodiments, R² is methyl orethyl. In some further such embodiments, R² is methyl. In some furthersuch embodiments, R² is ethyl. In some other embodiments of any of theaforementioned embodiments, R² is C₂₋₅ alkenyl. In some suchembodiments, R² is —CH₂—CH═CH₂ or —CH₂—CH═CH—CH₂—CH₃.

In some embodiments of any of the aforementioned embodiments, R² is nota hydrogen atom. In some such embodiments, a composition (according toany of the aspects or embodiments set forth below) comprising compoundsof formula (I) contains compounds of formula (I) having an Econfiguration around the carbon-carbon double bond to which R² isattached, and compounds of formula (I) having an Z configuration aroundthe carbon-carbon double bond to which R² is attached, wherein thecompounds of formula (I) having a Z configuration around thecarbon-carbon double bond to which R² is attached make up at least 1% byweight, or at least 2% by weight, or at least 5% by weight, or at least10% by weight, or at least 20% by weight, or at least 35% by weight, orat least 50% by weight, or at least 65% by weight, or at least 75% byweight, of compounds of formula (I) in the composition, based on thetotal weight of compounds of formula (I) in the composition.

In some embodiments of any of the aforementioned embodiments, n is aninteger from 6 to 50, or n is an integer from 6 to 30, or n is aninteger from 6 to 24, or n is an integer from 6 to 18, or n is aninteger from 8 to 16, or n is an integer from 9 to 15, or n is aninteger from 1 to 5, or n is an integer from 1 to 4, or n is an integerfrom 1 to 3, or n is an integer from 1 to 2.

Compositions Including Alkoxylated Unsaturated Fatty Acids

In some other aspects and embodiments, the disclosure providescompositions comprising: water and one or more compounds of theaforementioned aspects and embodiments.

In some such embodiments, the compositions further comprise one or moremonomers, such as monomers for forming synthetic latex materials, e.g.,using emulsion polymerization. In some embodiments, the one or moremonomers comprise free-radical-polymerizable monomers. For example, insome embodiments, the one or more monomers comprise monomers selectedfrom the group consisting of vinyl compounds (e.g., vinyl alcohol, vinylacetate, vinyl chloride, vinyl fluoride, and the like), acrylic acid,acrylates (e.g., alkyl acrylates, such as methyl acrylate, ethylacrylate, propyl acrylate, butyl acrylate, etc., and alkyl variousmethacrylates, such as methyl methacrylate, and the like), alkenes(e.g., ethylene, propylene, butadiene, and the like), halo-substitutedalkenes (e.g., vinyl chloride, vinyl fluoride, tetrafluoroethene, andthe like), nitrile-substituted alkenes (e.g., acrylonitrile, and thelike), styrene, and mixtures thereof.

In some embodiments, the composition is an emulsion having a dispersedphase and a continuous phase. In some embodiments, the continuous phasecomprises water. In some other embodiments, the dispersed phasecomprises at least a portion of the one or more monomers.

In some embodiments, the compositions include certain other materials.For example, in some embodiments, the composition further comprises afree radical initiator, e.g., which can initiate polymerization of theone or more monomers, and, in some embodiments, incorporation of thecompounds of formula (I) into the resulting polymer.

Other materials may also be included in the composition. For example, insome embodiments, the composition includes one or more additionalcomonomers. In some embodiments, the composition includes one or moresurfactants (in addition to the compounds of formula (I)). In some suchembodiments, the one or more surfactants are selected from the groupconsisting of anionic surfactants, ionic surfactants, nonionicsurfactants, and mixtures thereof. In some embodiments, the compositioncomprises one or more non-surfactant stabilizers. In some embodiments,the composition comprises one or more additives, such as chain transferagents, buffering agents, and salts.

Uses as Surfactants for Emulsion Polymerization

In other aspects and embodiments, the disclosure provides polymercompositions, which are formed from a reaction mixture, wherein thereaction mixture is a composition of any embodiments of the foregoingaspects and embodiments. In some embodiments, the polymer composition isa synthetic latex, e.g., which is formed by emulsion polymerization. Insome embodiments, the polymer composition is a synthetic rubber, e.g., astyrene-butadiene rubber.

In some other aspects and embodiments, the disclosure provides methodsof forming a polymer composition, the methods comprising: providing acomposition of the foregoing aspects and embodiments, such as those thatinclude one or more monomers; and reacting the one or more monomers inthe composition to form the polymer composition. In some embodiments,the polymer composition is a synthetic latex, e.g., which is formed byemulsion polymerization.

Other Uses

In other aspects and embodiments, the compounds of formula (I) can beput to a number of other uses and applications. These include, but arenot limited to, paint compositions, adhesive compositions, papercoatings, textile sizing, non-woven textiles, glass fibers sizingcompositions, binder compositions, floor polishes, inks, carpet backingmaterials, household cleaners, and laundry-related compositions.

In some aspects and embodiments, the disclosure provides compositions(e.g., aqueous compositions) for use in treating an oil or a gas wellthat include one or more compounds of formula (I). In some suchembodiments, the compositions also include other treatment compounds,such as terpenes (e.g., d-limonene) and/or unsaturated esters (e.g.,methyl 9-decenoate and/or methyl 9-dodecenoate).

In some aspects and embodiments, the disclosure provides cleaningcompositions comprising: water and one or more compounds of formula (I),where the composition is suitable for use in various cleaningapplications, such as hard-surface cleaning, and the like. In some suchaspects, the disclosure provides methods of cleaning comprising:providing a composition comprising water and one or more compounds offormula (I); and applying the composition to a surface to be cleaned. Insome embodiments, the surface is a hard surface.

In some aspects and embodiments, the disclosure provides fabric carecompositions comprising: water and one or more compounds of formula (I),where the composition is suitable for use in various fabric-careapplications, such as in laundry detergents, fabric softeners, and thelike. In some such aspects, the disclosure provides methods for treatingfabric, comprising: providing a composition comprising water and one ormore compounds of formula (I); and applying the composition to a fabricarticle.

In some aspects and embodiments, the disclosure provides personal carecompositions comprising: water and one or more compounds of formula (I),where the composition is suitable for use in various personal careapplications. In some embodiments, the compositions are in the form ofan emulsion, such as an oil-in-water or a water-in-oil emulsion. In somesuch aspects, the disclosure provides methods for treating mammalianskin or hair, comprising: providing a composition comprising water andone or more compounds of formula (I); and applying the composition tomammalian skin or hair. In some embodiments, the mammalian skin or hairis human skin or hair.

In some aspects and embodiments, the disclosure provides coatingcompositions comprising: water, a resin, and one or more compounds offormula (I). In some embodiments, the resin is a film-forming polymer.In some such embodiments, the film-forming polymer is a natural orsynthetic latex. In some other embodiments, the resin is an alkyd resin.In some such aspects, the disclosure provides methods for coating asurface, comprising: providing a composition comprising water, a resin,and one or more compounds of formula (I); and applying the compositionto a surface to be coated. In some embodiments, the resin is afilm-forming polymer. In some other embodiments, the resin is an alkydresin.

Derivation from Renewable Sources

The compounds employed in any of the aspects or embodiments disclosedherein can, in certain embodiments, be derived from renewable sources,such as from various natural oils or their derivatives. Any suitablemethods can be used to make these compounds from such renewable sources.Suitable methods include, but are not limited to, fermentation,conversion by bioorganisms, and conversion by metathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275595, and 2014/0275681, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above).

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described below with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above).

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The reactor design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

EXAMPLES Example 1 Synthetic Procedure

Into a 1 liter 3-necked round-bottomed flask equipped with a stir bar,thermocouple, Dean-Stark trap, condenser, glass stopper, heating mantle,and nitrogen inlet was added the fatty acid (9-decenoic acid, 9-DA, 75.0g, 0.440 mol). To this was added an equal molar amount of the methoxypolyethylene glycol (Carbowax™ 550, 252 g, 0.440 mol), toluene (325 g),and p-toluene sulfonic acid (pTsOH, 1.0 g). This was stirred (500 RPM)and heated to reflux (118 to 124° C.). Heating was continued until thetheoretical amount of water was collected in the Dean-Stark trap (7.9ml), usually after 8 hours. The water was drained from the Dean-Starktrap and the reaction continued (8 h) until no more water accumulated(<1.0 ml). During this time the reaction darkened to a yellow-orangecolor. Heating was discontinued and the cooled (60° C.) solution wastransferred into a 2 liter pear-shaped flask and concentrated in vacuo(95° C./full vacuum). The hot product (uC10MEE-12EO) was neutralized,transferred into a tared eight ounce clear bottle, and weighted(quantitative yield). Using a similar procedure, 7EO and 16EO variantsof the same ester were made.

Example 2 Foam Height

The 9-decenoic acid methyl ester ethoxylates (uC10MEE-XXEO) demonstratesignificantly lower foam generation than their saturated counterparts(C10MEE-XXEO), and lower foaming relative to commercial alkylphenolethoxylates (Table 1). Mitigation of surfactant-driven foaming is animportant trait that can impact the quality of finished coatings. Table1 shows foam height results using the Ross-Miles foam height method.

TABLE 1 Average Foam Height (cm) Surfactant Initial 1 min 3 min 5 minC10MEE-7EO 16.7 14.5 9.5 2.8 C10MEE-12EO 14.8 11.5 8.7 4.8 C10MEE-16EO13.5 11.7 9.0 4.8 uC10MEE-7EO 14.8 6.2 1.0 1.0 uC10MEE-12EO 14.2 7.7 1.51.0 uC10MEE-16EO 11.0 6.2 1.2 1.0

Example 3 Polymerization

9-Decenoic acid methyl ester ethoxylates show improved handlingcharacteristics relative to their saturated C10 counterparts. Manynonionic surfactants form intractable (gel) liquid crystalline phaseswith increasing aqueous concentration. This can be a significantlimitation not only in the preparation and transfer aqueous productscontaining these surfactants, but in maintaining their stability overprolonged periods. Methyl ester ethoxylates derived from 9-decenoic acidshowed no gel phase formation and lower viscosity than decanoic acidmethyl ester ethoxylates (Table 2). This is vastly improved relative tothe linear and other saturated alcohol ethoxylates used in lieu of APEs.Table 2 shows the Brookfield viscosity as a function of aqueousconcentration at 25° C.

TABLE 2 Viscosity (cP) as a Function of Aq. Concentration (Wt. %)Surfactant 10 20 30 40 50 60 70 80 C10MEE-7EO 3 7 15 30 48 44 39 37C10MEE-12EO 4 6 19 47 101 90 74 62 C10MEE-16EO 5 8 20 75 133 158 128 102uC10MEE-7EO 2 5 10 21 30 40 35 35 uC10MEE- 4 6 15 31 60 65 70 60 12EOuC10MEE- 7 10 16 48 85 83 75 79 16EO

Example 4 Polymerization

Into a 250 ml 4-necked round-bottomed flask (RBF) equipped with a stirbar, thermocouple, condenser, two rubber septa, hot water bath, andnitrogen inlet were added deionized (DI) water (45.6 g) and sodiumcarbonate (0.08 g). This was stirred (250 RPM) and warmed to 70° C.while nitrogen was being bubbled to degas the water. After 10 minutes,the nitrogen bubbling was discontinued and the anionic surfactant(PolyStep™ B-27, 2.4 g) was added followed by the nonionic surfactant(uC10MEE-12EO, 0.41 g) to obtain an HLB of 20.5. Separately, butylacrylate (9.0 g, 20 wt %) was mixed with vinyl acetate (36.0 g, 80 wt %)and added to a 50 ml glass syringe. A solution of potassium persulfate(0.040 g) was dissolved into DI water (1.0 g) and placed into a 1 mlglass syringe. Another solution of potassium persulfate (0.05 g) withsodium carbonate (0.10 g) was dissolved into DI water (6 ml) and placedinto a 5 ml glass syringe. The monomers were fed into the RBF by asyringe pump and the initial charge of the potassium persulfate solution(1.0 g) was added to the stirred surfactant solution. After 10 minutes,the other solution of initiator (6 ml) was pumped in and the reactiontemperature held at 70° C. +/−2° C. The monomer feed was complete after2 h, the initiator feed finished a half hour later and the reaction washeld at 70° C. for an additional hour. Heating was discontinued and thelatex was poured through a 600 micron screen to remove any coagulum. Thecoagulum was added to the residue in the flask and dried (1.9 g). Thewhite latex was weighted (92.6 g) and its percent solids determined(46.9 wt %, 43.4 g solids) to afford a 97.8% mass balance.

What is claimed is:
 1. A coating composition, the compositioncomprising: water; a resin; and a compound of formula (I)

wherein: R¹ is a hydrogen atom or C₁₋₆ alkyl; G¹ is C₁₋₄ alkylene R² isa hydrogen atom, C₁₋₅ alkyl, or C₂₋₅ alkenyl; and n is an integer from 1to
 50. 2. The composition of claim 1, wherein R¹ is a hydrogen atom. 3.The composition of claim 1, wherein R¹ is C₁₋₆ alkyl.
 4. The compositionof claim 1, wherein R¹ is methyl or ethyl.
 5. The composition of claim1, wherein G¹ is, independently at each occurrence, —CH₂—CH₂—,—CH₂—CH₂—CH₂—, —CH(CH₃)—CH₂—, —CH₂—CH(CH₃)—, or —CH₂—CH₂—CH₂—CH₂—. 6.The composition of claim 5, wherein G¹ is —CH₂—CH₂ at each occurrence.7. The composition of claim 1, wherein R² is a hydrogen atom.
 8. Thecomposition of claim 1, wherein R² is C₁₋₅ alkyl.
 9. The composition ofclaim 8, wherein R² is methyl or ethyl.
 10. The composition of claim 1,wherein R² is C₂₋₅ alkenyl.
 11. The composition of claim 10, wherein R²is —CH₂—CH═CH₂ or —CH₂—CH═CH—CH₂—CH₃.
 12. The composition of claim 1,wherein n is an integer from 6 to
 50. 13. The composition of claim 4,wherein n is an integer from 6 to
 50. 14. The composition of claim 6,wherein n is an integer from 6 to
 50. 15. The composition of claim 7,wherein n is an integer from 6 to
 50. 16. The composition of claim 1,wherein the resin is a film-forming polymer.
 17. The composition ofclaim 16, wherein the film-forming polymer is a natural or syntheticlatex.
 18. The composition of claim 1, wherein the resin is an alkydresin.
 19. A method for coating a surface, the method comprising:providing a composition of claim 1; and applying the composition to asurface to be coated.